Solvent extraction and separation of cobalt from leachate of spent lithium-ion battery cathodes with N263 in nitrite media

Abstract

To effectively separate and recover Co(II) from the leachate of spent lithium-ion battery cathodes, we investigated solvent extraction with quaternary ammonium salt N263 in the sodium nitrite system. NO₂ ⁻ combines with Co(II) to form an anion [Co(NO₂)₃]⁻, and it is then extracted by N263. The extraction of Co(II) is related to the concentration of NO₂ ⁻. The extraction efficiency of Co(II) reaches the maximum of 99.16%, while the extraction efficiencies of Ni(II), Mn(II), and Li(I) are 9.27%–9.80% under the following conditions: 30vol% of N263 and 15vol% of iso-propyl alcohol in sulfonated kerosene, the volume ratio of the aqueous-to-organic phase is 2:1, the extraction time is 30 min, and 1 M sodium nitrite in 0.1 M HNO₃. The theoretical stages require for the Co(II) extraction are performed in the McCabe—Thiele diagram, and the extraction efficiency of Co(II) reaches more than 99.00% after three-stage counter-current extraction with Co(II) concentration of 2544 mg/L. When the HCl concentration is 1.5 M, the volume ratio of the aqueous-to-organic phase is 1:1, the back-extraction efficiency of Co(II) achieves 91.41%. After five extraction and back-extraction cycles, the Co(II) extraction efficiency can still reach 93.89%. The Co(II) extraction efficiency in the actual leaching solution reaches 100%.

Keywords

cobalt / N263 / sodium nitrite / extraction / iso-propyl alcohol / spent lithium-ion battery

References

[1] Peek E, Åkre T, Asselin E. Technical and business considerations of cobalt hydrometallurgy. JOM, 2009, 61(10): 43.

[2] Q. Dehaine, L.T. Tijsseling, H.J. Glass, T. Törmänen, and A.R. Butcher, Geometallurgy of cobalt ores: A review, Miner. Eng., 160(2021), art. No. 106656.

[3] Chandra M, Yu DW, Tian QH, Guo XY. Recovery of cobalt from secondary resources: A comprehensive review. Miner. Process. Extr. Metall. Rev., 2022, 43(6): 679.

[4] Wassink B, Dreisinger D, Howard J. Solvent extraction separation of zinc and cadmium from nickel and cobalt using Aliquat 336, a strong base anion exchanger, in the chloride and thiocyanate forms. Hydrometallurgy, 2000, 57(3): 235.

[5] Golmohammadzadeh R, Faraji F, Rashchi F. Recovery of lithium and cobalt from spent lithium ion batteries (LIBs) using organic acids as leaching reagents: A review. Resour. Conserv. Recycl., 2018, 136, 418.

[6] Tran MK, Rodrigues MTF, Kato K, Babu G, Ajayan PM. Deep eutectic solvents for cathode recycling of Li-ion batteries. Nat. Energy, 2019, 4(4): 339.

[7] Wang WY, Yen CH, Hsu JK. Selective recovery of cobalt from the cathode materials of NMC type Li-ion battery by ultrasound-assisted acid leaching and microemulsion extraction. Sep. Sci. Technol., 2020, 55(16): 3028.

[8] Zheng XH, Zhu ZW, Lin X, et al. A mini-review on metal recycling from spent lithium ion batteries. Engineering, 2018, 4(3): 361.

[9] Zeng XL, Li JH, Singh N. Recycling of spent lithium-ion battery: A critical review. Crit. Rev. Environ. Sci. Technol., 2014, 44(10): 1129.

[10] Gu F, Guo JF, Yao X, Summers PA, Widijatmoko SD, Hall P. An investigation of the current status of recycling spent lithium-ion batteries from consumer electronics in China. J. Clean. Prod., 2017, 161, 765.

[11] Sun L, Qiu KQ. Organic oxalate as leachant and precipitant for the recovery of valuable metals from spent lithium-ion batteries. Waste Manage., 2012, 32(8): 1575.

[12] Bernardes AM, Espinosa DCR, Tenório JAS. Recycling of batteries: A review of current processes and technologies. J. Power Sources, 2004, 130(1–2): 291.

[13] Li L, Ge J, Chen RJ, Wu F, Chen S, Zhang XX. Environmental friendly leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries. Waste Manage., 2010, 30(12): 2615.

[14] Xu JQ, Thomas HR, Francis RW, Lum KR, Wang JW, Liang B. A review of processes and technologies for the recycling of lithium-ion secondary batteries. J. Power Sources, 2008, 177(2): 512.

[15] Chen L, Tang XC, Zhang Y, Li LX, Zeng ZW, Zhang Y. Process for the recovery of cobalt oxalate from spent lithium-ion batteries. Hydrometallurgy, 2011, 108(1–2): 80.

[16] Freitas MBJG, Celante VG, Pietre MK. Electrochemical recovery of cobalt and copper from spent Li-ion batteries as multilayer deposits. J. Power Sources, 2010, 195(10): 3309.

[17] Kang JG, Senanayake G, Sohn J, Shin SM. Recovery of cobalt sulfate from spent lithium ion batteries by reductive leaching and solvent extraction with Cyanex 272. Hydrometallurgy, 2010, 100(3–4): 168.

[18] Wang HY, Huang K, Zhang Y, et al. Recovery of lithium, nickel, and cobalt from spent lithium-ion battery powders by selective ammonia leaching and an adsorption separation system. ACS Sustainable Chem. Eng., 2017, 5(12): 11489.

[19] Chen XP, Chen YB, Zhou T, Liu DP, Hu H, Fan SY. Hydrometallurgical recovery of metal values from sulfuric acid leaching liquor of spent lithium-ion batteries. Waste Manage., 2015, 38, 349.

[20] Ocaña N, Alguacil FJ. Cobalt—manganese separation: The extraction of cobalt(II) from manganese sulphate solutions by cyanex 301. J. Chem. Technol. Biotechnol., 1998, 73(3): 211.

[21] Pośpiech B, Walkowiak W. Separation of copper(II), co-balt(II) and nickel(II) from chloride solutions by polymer inclusion membranes. Sep. Purif. Technol., 2007, 57(3): 461.

[22] Blitz-Raith AH, Paimin R, Cattrall RW, Kolev SD. Separation of cobalt(II) from nickel(II) by solid-phase extraction into Aliquat 336 chloride immobilized in poly(vinyl chloride). Talanta, 2007, 71(1): 419.

[23] Kao HC, Juang RS. Kinetic analysis of non-dispersive solvent extraction of concentrated Co(II) from chloride solutions with Aliquat 336: Significance of the knowledge of reaction equilibrium. J. Membr. Sci., 2005, 264(1–2): 104.

[24] Majdan M, Mierzwa J, Sadowski P. On the separation of Co and Ni from chloride media with Aliquat 336-TBP and Aliquat 336-TOPO. Monatsh. Chem., 1997, 128(2): 113.

[25] N.A. Milevskii, I.V. Zinov’eva, Y.A. Zakhodyaeva, and A.A. Voshkin, Separation of Li(I), Co(II), Ni(II), Mn(II), and Fe(III) from hydrochloric acid solution using a menthol-based hydrophobic deep eutectic solvent, Hydrometallurgy, 207(2022), art. No. 105777.

[26] Wei YZ, Arai T, Kumagai M, Feng QM. Adsorption behavior of various metal ions in nitrite medium and separation of some metals by anion exchange. J. Ion Exch., 2003, 14, 305. Suppl.

[27] H. Chen, S. Gu, Y.X. Guo, et al., Leaching of cathode materials from spent lithium-ion batteries by using a mixture of ascorbic acid and HNO₃, Hydrometallurgy, 205(2021), art. No. 105746.

[28] Ju JR, Feng YL, Li HR, et al. Separation of Cu, Co, Ni and Mn from acid leaching solution of ocean cobalt-rich crust using precipitation with Na₂S and solvent extraction with N₂₃₅. Korean J. Chem. Eng., 2022, 39(3): 706.

[29] Yang YJ, Yang YN, He CL, et al. The adsorption and desorption behavior and mechanism research of cobalt, nickel and copper in nitrite—sulfuric acid system. Sep. Sci. Technol., 2022, 57(12): 1848.

[30] Z.S. Liu, J. Huang, Y.M. Zhang, et al., Separation and recovery of vanadium and aluminum from oxalic acid leachate of shale by solvent extraction with Aliquat 336, Sep. Purif. Technol., 249(2020), art. No. 116867.

[31] K. Wang, G.Q. Zhang, M.Z. Luo, and M. Zeng, Separation of Co and Mn from acetic acid leaching solution of spent lithiumion battery by Cyanex272, J. Environ. Chem. Eng., 10(2022), No. 5, art. No. 108250.

[32] Nayl AA, Hamed MM, Rizk SE. Selective extraction and separation of metal values from leach liquor of mixed spent Li-ion batteries. J. Taiwan Inst. Chem. Eng., 2015, 55, 119.

[33] Rizk HE, El-Nadi YA, El-Hefny NE. Extractive separation of scandium from strongly alkaline solution by quaternary ammonium salt. Solvent Extr. Ion Exch., 2020, 38(3): 350.

[34] Zhang H, Li CM, Chen XJ, et al. Layered ammonium vanadate nanobelt as efficient adsorbents for removal of Sr²⁺ and Cs⁺ from contaminated water. J. Colloid Interface Sci., 2022, 615, 110.

[35] J.J. Meng, C.L. He, Y.J. Li, et al., Enhanced adsorption and separation of gallium using silica-based P507-TBP/SiO₂-P adsorbent from sulfuric acid solution, Microporous Mesoporous Mater., 314(2021), art. No. 110859.

[36] Jiao LZ, Dong DM, Zheng WG, et al. Determination of nitrite using UV absorption spectra based on multiple linear regression. Asian J. Chem., 2013, 25(4): 2273.

[37] Benalia H, Barkat D. Solvent extraction studies of cobalt(II) by capric acid from sodium sulfate solution. J. Dispersion Sci. Technol., 2017, 38(9): 1247.

[38] Cañón J, Teplyakov AV. XPS characterization of cobalt impregnated SiO ₂ and γ-Al₂O₃. Surf. Interface Anal., 2021, 53(5): 475.

[39] G. Kowalski, J. Pielichowski, and M. Grzesik, Characteristics of polyaniline cobalt supported catalysts for epoxidation reactions, Sci. World J., 2014(2014), art. No. 648949.